Month: February 2023

Gold(I)-Catalyzed Stereoselective Olefin Cyclopropanation was written by Johansson, Magnus J.;Gorin, David J.;Staben, Steven T.;Toste, F. Dean. And the article was included in Journal of the American Chemical Society in 2005.Application In Synthesis of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine This article mentions the following:

A triphenylphosphinegold(I)-catalyzed cyclopropanation of olefins using propargyl esters as gold(I)-carbene precursors is reported. This reaction provided the basis for the use of a DTBM-SEGPHOS gold(I) complex as a catalyst in the enantioselective (up to 94% ee) preparation of vinylcyclopropanes with high cis-selectivity. In the experiment, the researchers used many compounds, for example, (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9Application In Synthesis of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine).

(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9) belongs to chiral phosphine ligands. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these reactions have evolved relatively slowly. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Application In Synthesis of (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Catalytic Enantioselective Synthesis of γ-Lactams with β-Quaternary Centers via Merging of C-C Activation and Sulfonyl Radical Migration was written by Yu, Xuan;Zhang, Zining;Dong, Guangbin. And the article was included in Journal of the American Chemical Society in 2022.Application of 133545-16-1 This article mentions the following:

To expand the repertoire of C-C activation, here the discovery of a Rh-catalyzed enantioselective C-C activation involving migration of a sulfonyl radical were described. This reaction directly transforms cyclobutanones containing a sulfonamide-tethered 1,3-diene moiety into γ-lactams containing a β-quaternary center with excellent enantioselectivity. This unusual process involved cleavage of C-C and N-S bonds and subsequent formation of C-N and C-S bonds. The reaction also exhibited broad functional group tolerance and a good substrate scope. A combined exptl. and computational mechanistic study suggested that the reaction goes through a Rh(I)-mediated oxidative addition into the cyclobutanone C-C bond followed by a Rh(III)-triggered N-S bond homolysis and sulfonyl radical migration. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Application of 133545-16-1).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Trivalent phosphorus compounds called phosphines have a tetrahedral electron-group geometry which makes them structurally analogous to amines.Application of 133545-16-1

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

A Practical, Enantioselective Synthesis of the Fragrances Canthoxal and Silvial, and Evaluation of Their Olfactory Activity was written by Beghetto, Valentina;Scrivanti, Alberto;Bertoldini, Matteo;Aversa, Manuela;Zancanaro, Aurora;Matteoli, Ugo. And the article was included in Synthesis in 2015.Computed Properties of C74H104O6P2 This article mentions the following:

Fragrances (S)-(+)-canthoxal, (R)-(-)-canthoxal [i.e., (S)-(+)-3-(4-methoxyphenyl)-2-methylpropanal, (R)-(-)-3-(4-methoxyphenyl)-2-methylpropanal] and (+)-Silvial and (-)-Silvial were synthesized in high enantiopurity by a simple four-step strategy starting from the com. available 4-substituted benzaldehydes. The key synthetic step is the catalytic asym. hydrogenation of the appropriate 3-aryl-2-(methyl)acrylic acid which has been carried out employing an in situ prepared ruthenium/axially chiral phosphine catalyst (up to 98% ee). The olfactory activity of the single enantiomers was evaluated. Under optimized conditions the synthesis of the target compounds was achieved using 1,1′-[(1S)-6,6′-dimethoxy[1,1′-biphenyl]-2,2′-diyl]bis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] [i.e., (S)-3,5-di-tert-butyl-4-MeOBIPHEP] and bis(η⁶-benzene)di-μ-(chloro)dichlorodiruthenium as ligand-catalyst combination. The tilte compounds thus formed included (αS)-5-methoxyα-methylbenzenepropanal [i.e., (+)-(S)-canthoxal] and (αR)-5-methoxyα-methylbenzenepropanal [i.e., (-)-(R)-canthoxal]. Silvial enantiomers included (-)-α-methyl-4-(2-methylpropyl)benzenepropanal [i.e., (-)-Silvial] and (+)-α-methyl-4-(2-methylpropyl)benzenepropanal [i.e., (+)-Silvial]. Other catalysts included (1S,1′S)-1,1′-bis[bis(4-methoxy-3,5-dimethylphenyl)phosphino]-2,2′-bis[(R)-(dimethylamino)phenylmethyl]ferrocene [(RS)-MandyPhos], 1,1′-[(1S)-6,6′-dimethoxy[1,1′-biphenyl]-2,2′-diyl]bis[1,1-diphenylphosphine [(S)-MeOBIPHEP], 1,1′-[(1R)-[1,1′-binaphthalene]-2,2′-diyl]bis[1,1-diphenylphosphine] [(R)-BINAP]. In the experiment, the researchers used many compounds, for example, (R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9Computed Properties of C74H104O6P2).

(R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9) belongs to chiral phosphine ligands. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these reactions have evolved relatively slowly. Trivalent phosphorus compounds called phosphines have a tetrahedral electron-group geometry which makes them structurally analogous to amines.Computed Properties of C74H104O6P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-catalyzed DYKAT of vinyl epoxides: Enantioselective total synthesis and assignment of the configuration of (+)-broussonetine G was written by Trost, Barry M.;Horne, Daniel B.;Woltering, Michael J.. And the article was included in Angewandte Chemie, International Edition in 2003.HPLC of Formula: 174810-09-4 This article mentions the following:

A potential general approach to potent N-heterocyclic glycosidase inhibitors is illustrated by the first total synthesis of (+)-broussonetine G. The key transformation of the synthesis relies on two successive palladium-catalyzed asym. allylic alkylations of butadiene monoxide with a nitrogen nucleophile to construct the pyrrolidine core. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4HPLC of Formula: 174810-09-4).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) belongs to chiral phosphine ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.HPLC of Formula: 174810-09-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Nonenzymatic kinetic resolution of secondary alcohols: enantioselective S_N2 displacement of hydroxy groups by halogens in the presence of chiral BINAP was written by Sekar, Govindasamy;Nishiyama, Hisao. And the article was included in Journal of the American Chemical Society in 2001.Quality Control of (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) This article mentions the following:

Cyclic secondary alcs. I (R = Ph, 2-MeC₆H₄, 3-MeC₆H₄, 4-MeC₆H₄, 4-MeOC₆H₄, 1-naphthyl, 2-naphthyl, cyclohexyl), phenylcyclooctanol II, and 1-phenyl-2-octadecanol undergo kinetic resolution by stereoselective nucleophilic displacement of secondary alcs. with chlorides in the presence of (S)-BINAP to give unreacted alcs. such as III in 82-97% yields and 69-98% ee and the inverted secondary chlorides IV in 56-94% ee. E.g., dehydrated THF was added to a mixture of I (R = Ph), 1 equivalent N-chlorosuccinimide, and 0.3 equivalent (S)-BINAP and the mixture stirred until the solution became clear; workup and chromatog. yielded (1R,2S)-III in 40% yield and 85% ee and (1R,2R)-IV in 42% yield and 89% ee in addition to the P,P’-dioxide of (S)-BINAP which was recovered in 92%. The enantioselectivity of the resolution was highly dependent upon the solvent used and the amount of chlorinating agent used; THF was the optimal solvent for the process and N-chlorosuccinimide as the chlorinating agent. In the experiment, the researchers used many compounds, for example, (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5Quality Control of (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine)).

(((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Over the last decade, however, and especially since 2005, considerable progress has been made in asymmetric phosphine catalysis.Quality Control of (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-Catalyzed Enantioselective Arylation of Racemic Ketones to Form Bridged Bicycles via Dynamic Kinetic Resolution was written by Huang, Xiaolei;Oh, William Ray Jun Jie;Zhou, Jianrong Steve. And the article was included in Angewandte Chemie, International Edition in 2018.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

Enantioselective α-arylation of racemic ketones containing existing α’-stereocenters is reported for the first time via base-induced dynamic kinetic resolution Bridged bicyclic rings are formed in good ee values, which are difficult to obtain otherwise. Furthermore, reactions in DMSO-d₆ resulted in extensive deuteration of both α- and α’-positions in the products, thus supporting a pathway involving rapid, reversible deprotonation of ketones under catalytic conditions. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Regioselective hydroesterification of styrene catalyzed by cationic palladium(II) complexes under mild conditions was written by Oi, S.;Nomura, M.;Aiko, T.;Inoue, Y.. And the article was included in Journal of Molecular Catalysis A: Chemical in 1997.Electric Literature of C33H25OP This article mentions the following:

The cationic palladium(II) complex [Pd(MeCN)₂(PPh₃)₂](BF₄)₂ was found to be an active catalyst for hydroesterification (alkoxycarbonylation) of styrene using CO and methanol under very mild conditions. The system, Pd(OAc)₂-PPh₃–p-toluenesulfonic acid, which should give rise to a cationic species in situ, was also effective to produce the branched ester regioselectively in an excellent yield at ambient temperature Asym. hydroesterification of styrene by the use of chiral phosphines as ligands was also studied. The hydroesterification of 4-isobutylstyrene gave α-methyl-4-(2-methylpropyl)benzeneacetic acid Me ester (i.e., ibuprofen Me ester). Also prepared was (S)-6-methoxy-α-methyl-2-naphthaleneacetic acid Me ester. In the experiment, the researchers used many compounds, for example, (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9Electric Literature of C33H25OP).

(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Indeed, very little research on chiral tertiary phosphine-catalyzed asymmetric reactions occurred prior to the year 2000.Electric Literature of C33H25OP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric allylation of aryl aldehydes: studies on the scope and mechanism of the palladium catalyzed diethylzinc mediated umpolung using phosphoramidite ligands was written by Howell, Gareth P.;Minnaard, Adriaan J.;Feringa, Ben L.. And the article was included in Organic & Biomolecular Chemistry in 2006.Product Details of 185449-81-4 This article mentions the following:

Using modular, monodentate phosphoramidite ligands, enantioselective palladium catalyzed diethylzinc mediated allylation of aldehydes was achieved. The scope of the asym. C-C bond formation was investigated with respect to nucleophilic and electrophilic components and an alternative reaction mechanism is proposed based on our findings. In the experiment, the researchers used many compounds, for example, (S)-4-(Dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)morpholine (cas: 185449-81-4Product Details of 185449-81-4).

(S)-4-(Dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)morpholine (cas: 185449-81-4) belongs to chiral phosphine ligands. Thousands of arylphosphines have been used as chiral ligands for metal-catalyzed asymmetric reactions. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Product Details of 185449-81-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Synthesis of novel chiral phosphine-olefin complexes and their evaluation as ligands in the rhodium-catalyzed asymmetric 1,4-addition was written by Stemmler, Rene T.;Bolm, Carsten. And the article was included in Synlett in 2007.COA of Formula: C26H28FeNP This article mentions the following:

Novel chiral phosphine-olefin complexes containing ferrocene and cyrhetrene backbones were synthesized and evaluated as ligands in the Rh-catalyzed 1,4-addition of phenylboronic acid to cyclohexenone. The highest efficiency in this series was observed with planar-chiral ligands (S_p)-1-(diphenylphosphino)-2-vinylferrocene and (S_p)-tricarbonyl[η⁵-1-(diphenylphosphino)-2-ethenylcyclopentadienyl]rhenium, which furnished the corresponding product with up to 71% ee. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2COA of Formula: C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.COA of Formula: C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-catalyzed DYKAT of butadiene mono-epoxide: enantioselective total synthesis of (+)-DMDP, (-)-bulgecinine, and (+)-broussonetine G was written by Trost, Barry M.;Horne, Daniel B.;Woltering, Michael J.. And the article was included in Chemistry – A European Journal in 2006.SDS of cas: 174810-09-4 This article mentions the following:

Palladium catalyzed DYKAT (dynamic kinetic asym. transformation) allylic alkylation reaction of an amine with two equivalent of butadiene monoxide allows for the expedient synthesis of trans- and cis-2,5-dihydropyrroles. The versatility of these chiral synthons towards the synthesis of a wide variety of imino-sugar natural products was demonstrated with the short and high yielding asym. syntheses of (+)-DMDP, and (-)-bulgecinine. In addition, the first total synthesis of (+)-broussonetine G, a potent glycosidase inhibitor, is described along with the assignment of its relative and absolute stereochem. configuration. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4SDS of cas: 174810-09-4).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Over the last decade, however, and especially since 2005, considerable progress has been made in asymmetric phosphine catalysis.SDS of cas: 174810-09-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis